(I) Field of the Invention
The present invention relates to the general field of catalysts and processes applicable to the conversion of hydrocarbons particularly the conversion of heavy oils contaminated with substantial amounts of metals and carbon e.g. reduced crudes.
In the evolution of catalytic cracking, the process has gradually evolved from a hardware standpoint, until it has reached its present state of develoment in fluid catalytic cracking of vacuum gas oils. However, some of the considerable advances in hardware have come about as a result of the introduction of new and very unique catalysts (namely the introduction of the zeolite catalyst which enabled the hardware to evolve to riser cracking with very short contact times).
Likewise, in reduced crude conversion of carbometallic oils, a process has been developed (Myers, Busch U.S. Pat. No. 4,299,687) with all its attendant hardware, designed to facilitate the conversion of these high boiling residues into high octane gasoline with low capital investment and operating costs. However, it was fully appreciated that in order to realize the tremendous potential volume conversion to liquid transportation products existant in reduced crude, that highly selective catalysts would be required.
As pointed out in our letter to the editor of Science (reference 1980) it has been the intent of research to evolve a catalyst which could, in this process, utilize all the hydrogen and carbon in a most efficient manner. It was pointed out in that article that there is sufficient hydrogen available so as to convert all of reduced crude into a combination of toluene and pentenes in greater than 100 volume % yield, and with high octanes over 100, and that the only limiting factor to achieving such a result was the catalyst.
With that realization in mind, the inventors of this new catalyst have sought by very intensive research means to create a catalyst which, when harnessed with the unique features of the reduced crude conversion process, serve to obtain a yield of liquid transportation products previously not considered possible. In order to achieve this objective, it has been necessary that all aspects of catalytic conversion be considered and that all those properties required to reduce coke and hydrogen production, increase gasoline and light cycle oil yield, immobilize or reduce the effect of vanadia, inhibit the adverse effects of nickel, facilitate cracking in the presence of high molecular weight molecules so as to achieve cracking in the sieve, and also to operate in the presence of high molecular weight basic nitrogen compounds which tend to neutralize acid sites be optimized. In our invention, all of these features were concentrated on, and optimized, so as to produce a metal resistant, high performance catalyst to be harnessed with this new reduced crude conversion process.
(II) Description of the Prior Art
Because of the economic importance of the field of the present invention, a number of patent applications and technical publications have been addressed to the search for catalysts which will provide the most valuable product distribution while maintaining their activity and which are produceable at reasonable cost. The Assignee of the present application has itself directed substantial activity to the field of heavy oil conversion and its patents and pending applications include:
U.S. Pat. No. 4,341,624 to George D. Myers PA1 U.S. Pat. No. 4,347,122 to George D. Myers et al PA1 U.S. Pat. No. 4,299,687 to George D. Myers et al. PA1 U.S. Pat. No. 4,354,923 to George D. Myers et al PA1 U.S. Pat. No. 4,332,673 to George D. Myers PA1 U.S. Pat. No. 4,508,839 to W. P. Hettinger, Jr. et al PA1 U.S. Pat. No. 4,407,714 to W. P. Hettinger, Jr. et al. PA1 "New Generation of FCC Catalyst", E. J. Demmel and J. C. Lim, API Proceedings, Vol. 58, Pg. 29-32, April 1975 PA1 reduce and minimize coke and hydrogen production, PA1 maximize gasoline and light cycle oil yield, immobilize or reduce the effect of vanadia, inhibit or reduce the adverse effect of nickel, facilitate cracking in the presence of high molecular weight molecules so as to achieve cracking in the sieve, PA1 operate in the presence of high molecular weight basic nitrogen compounds which tend to neutralize acid sites, PA1 operate in the presence of large coking molecules such as asphaltenes, without allowing these macro molecules to block access of smaller molecules to catalyst sites. PA1 be economically acceptable. PA1 A. Low catalytic coke production; PA1 B. High light catalytic cycle oil (LCO) to slurry oil (Slurry) ratio in products; PA1 C. Excellent resistance to metal contamination and poisoning; PA1 D. Excellent cracking activity in the presence of high metals containing feedstocks; PA1 E. Stability under high temperatures permitting severe regeneration conditions to remove the high amounts of carbon laid down by residual oils; PA1 F. high gasoline selectivity and production; PA1 G. low slurry production; PA1 H. high octane gasoline; PA1 I. Good resistance in terms of catalytic cracking of high basic nitrogen containing feedstocks; PA1 J. High activity while exposed to large asphaltene molecules. PA1 K. Is acceptably low in cost.
Filtrol Corporation patents and literature include:
______________________________________ U.S. Pat. No. 4,058,484 Alafandi NH.sub.4 - faujasite U.S. Pat. No. 4,085,069 Alafandi NH.sub.4 - faujasite in a matrix U.S. Pat. No. 4,086,187 Lim attrition resistant catalyst U.S. Pat. No. 4,100,108 Alafandi 2 zeolites in matrix U.S. Pat. No. 4,192,778 Alafandi RE exchanged faujasite U.S. Pat. No. 4,198,319 Alafandi faujasite + Si--Al gel (50-70% SiO.sub.2) + clay U.S. Pat. No. 4,206,085 Lim faujasite + Al.sub.2 O.sub.3 + silica sol U.S. Pat. No. 4,215,016 Alafandi NaY + cations exchange at &lt;500.degree. F. under pressure U.S. Pat. No. 4,234,457 Alafandi RE exchange of Si--AL matrix U.S. Pat. No. 4,252,684 Alafandi RE exchange of Si--AL matrix U.S. Pat. No. 4,224,188 Alafandi exchange of NaY with Al ion, then NH.sub.4 ion U.S. Pat. No. 4,228,137 Taylor produce faujasite by seeding with clay from halloysite U.S. Pat. No. 4,237,031 Alafandi RE exchange of ammonium Si--Al matrix under temp-pressure U.S. Pat. No. 4,246,138 Alafandi RE exchange of ammonium Si--Al matrix under temp-pressure U.S. Pat. No. 4,259,210 Alafandi RE exchange of ammonium Si--Al matrix under temp-pressure U.S. Pat. No. 4,142,995 Alafandi RE faujasite in Si--Al matrix U.S. Pat. No. 4,253,989 Lim REY + Clay + Al.sub.2 O.sub.3 + 0.5-3.5% SiO.sub.2 U.S. Pat. No. 4,269,815 Lim NaY - multiple exchange with NH.sub.4 under temp-pressure U.S. Pat. No. 4,310,441 Alafandi large pore Si--Al from cationic to anionic Al sources with 0.6 cc/g PV in 20-600 A range U.S. Pat. No. 4,325,845 Lim zeolite in matrix (clay + silica gel from Na silicate) U.S. Pat. No. 4,325,847 Lim zeolite in matrix (pseudoboehmite + alumina gel) U.S. Pat. No. 4,333,857 Lim zeolite &lt; 3 microns in matrix of pseudoboehmite, clay, silica sol ______________________________________